Bleaching composition

ABSTRACT

Bleach compositions comprising a percarbonate bleach and an amino tricarboxylic acid exhibit a reduced tendency to deposit calcium carbonate insolubles on substrates being bleached. Laundry compositions comprising percarbonate bleach and methyl glycine diacetic acid are provided.

TECHNICAL FIELD

The present invention relates to a bleaching composition adapted for usein a cleaning method, exhibiting improved soil and stain removal.

BACKGROUND TO THE INVENTION

Compositions designed for use in cleaning, particularly in automaticdishwashing and laundry methods are well known and a consistent efforthas been made by detergent manufacturers to improve the cleaning and/orrinsing efficiency of said compositions as reflected by many patentpublications.

The satisfactory removal of bleachable soils such as tea, coffee and redwine is a particular challenge to the formulator of a bleachingcomposition. Traditionally, the removal of such bleachable stains hasbeen enabled by the use of bleach components such as oxygen bleaches,including hydrogen peroxide and organic peroxyacids. The organicperoxyacids are often obtained by the in situ perhydrolysis reactionbetween hydrogen peroxide and an organic peroxyacid bleach precursor.

Traditionally, the most commonly used source of hydrogen peroxide hasbeen perborate salts, such as sodium perborate monohydrate andtetrahydrate. Percarbonate salts, such as sodium percarbonate arealternative hydrogen peroxide sources which have the advantage of, afterrelease of the hydrogen peroxide, additionally providing carbonate ionsto the wash solution. Carbonate ions contribute alkalinity and buildercapacity to the solution.

A problem associated with the use of percarbonate bleach is theformation of insoluble carbonate deposits. It is believed that carbonateions released by the percarbonate bleach during perhydrolysis, complexwith cations in the wash solution forming insoluble carbonate deposits.Additionally, once having formed, an initial minor carbonate deposit canact as a "seeding centre" for the formation of a larger, possiblycomposite, deposit structures, including those associated withredeposition of soils, lime soaps and silicate salts.

Lime soap deposits are most commonly encountered when the washloadcontains fatty soils, which naturally contain levels of free fattyacids, and when lipolytic enzymes are components of the formulation.Lipolytic enzymes catalyse the degradation of fatty soils into freefatty acids and glycerol. Silicate is a common component of machinedishwashing formulations, where it is added for its china carecapability.

Deposit formation can occur on a range of commonly encountered substratesurfaces including fabric, plastic, glass, metal and china surfaces.Certain deposit types however, show a greater propensity to deposit oncertain substrates.

The formation of insoluble carbonate, especially calcium carbonate,deposits are a particular problem in the machine dishwashing art. Suchdeposits are also problematic in laundry washing methods, where thedeposits accumulate on the fabric surface (a phenomenon sometimes knownas `ash deposition`) thereby causing the fabrics to take on a yellowedor dingy appearance.

The naturally sourced, inlet water to the dishwasher machine can be asufficient source of Ca²⁺ and Mg²⁺ ions and CO₃ ²⁻ /HCO₃₋ ions to makedeposit formation a problem. Whilst the salt softening system, throughwhich the inlet water will pass prior to entry into the main cavity of adishwasher machine, can be efficient at removing the naturally presentCa²⁺ and Mg²⁺ ions it is inefficient at removing the CO₃ ²⁻ /HCO₃₋ ionswhich therefore enter into the wash/rinse solution.

The Applicants have now established that both the levels of Ca²⁺ /Mg²⁺hardness ions and the levels of CO₃ ²⁻ /HCO₃₋ ions in the wash/rinsewater of a dishwasher machine are factors controlling calcium carbonatedeposit formation. Critical levels of all components must be exceededfor deposit formation to occur. These critical levels are to an extentinterdependent. Thus, even in wash/rinse solutions containing highlevels of one component, deposit formation will not occur in the absenceof the critical level of the other component.

The Applicants have found that the problem of calcium carbonate depositformation associated with the use of a percarbonate bleach, may beeffectively ameliorated by the inclusion of amino tricarboxylic acid(ATCA) into a bleaching formulation.

SUMMARY OF THE INVENTION

According to the present invention there is provided a bleachingcomposition comprising

(a) a percarbonate bleach compound; and

(b) an amino tricarboxylic acid or salt thereof wherein said aminotricarboxylic acid has the general formula: ##STR1## where R₁, R₂ and R₃are alkyl groups or substituted alkyl groups of chain length C1 to C4; nis 0 or 1; and X is an organic substituent group.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a bleaching composition adapted for usein a cleaning method, exhibiting improved soil and stain removal.

Percarbonate Bleach

This invention has as an essential component a percarbonate bleachcompound. Alkali metal or alkaline earth metal percarbonates,particularly sodium percarbonate are preferred percarbonates forinclusion in compositions in accordance with the invention. Sodiumpercarbonate is an addition compound having a formula corresponding to2Na₂ CO₃.3H₂ O₂, and is available commercially as a crystalline solid.Commercial suppliers include Solvay, FMC, Tokai Denka and others.

The percarbonate compound can be present at levels of between 1% and50%, preferably between 2% and 30%, most preferably between 3% and 20%by weight of detergent composition.

The percarbonate is most preferably incorporated into such compositionsin a coated form which provides in-product stability.

A suitable coating material providing in product stability comprisesmixed salt of a water soluble alkali metal sulphate and carbonate. Suchcoatings together with coating processes have previously been describedin GB-1,466,799, granted to Interox on Mar. 9, 1977. The weight ratio ofthe mixed salt coating material to percarbonate lies in the range from1:200 to 1:4, more preferably from 1:99 to 1:9, and most preferably from1:49 to 1:19. Preferably, the mixed salt is of sodium sulphate andsodium carbonate which has the general formula Na₂ SO₄.n.Na₂ CO₃ whereinn is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferablyn is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts orboric acids or other inorganics), waxes, oils, fatty soaps can also beused advantageously within the present invention.

Oxygen-releasing Bleaching System

In one preferred aspect the bleaching composition contains thepercarbonate bleach compound as a hydrogen peroxide source and anorganic peroxyacid bleach precursor compound. The production of theorganic peroxyacid occurs by an in situ reaction of the precursor with asource of hydrogen peroxide. Alternative sources of hydrogen peroxideinclude inorganic perhydrate bleaches. In a preferred aspect a preformedorganic peroxyacid is incorporated directly into the composition.Compositions containing mixtures of a hydrogen peroxide source andorganic peroxyacid precursor in combination with a preformed organicperoxyacid are also envisaged.

Peroxyacid Bleach Precursor

A highly preferred component of the bleaching composition is aperoxyacid bleach precursor. Peroxyacid bleach precursors are compoundswhich react with hydrogen peroxide in a perhydrolysis reaction toproduce a peroxyacid. Generally peroxyacid bleach precursors may berepresented as ##STR2## where L is a leaving group and X is essentiallyany functionality, such that on perhydrolysis the structure of theperoxyacid produced is ##STR3##

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 10% byweight, most preferably from 1.5% to 5% by weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a widerange of classes. Suitable classes include anhydrides, esters, imides,lactams and acylated derivatives of imidazoles and oximes. Examples ofuseful materials within these classes are disclosed in GB-A-1586789.Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of: ##STR4##and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup. Any of R¹, R³ and R⁴ my be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen,amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are --SO₃ ⁻ M⁺, --CO₂ ⁻ M⁺, --SO₄ ⁻M⁺, --N⁺ (R³)₄ X⁻ and O←N(R³)₃ and most preferably --SO₃ ⁻ M⁺ and --CO₂⁻ M⁺ wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, Mis a cation which provides solubility to the bleach activator and X isan anion which provides solubility to the bleach activator. Preferably,M is an alkali metal, ammonium or substituted ammonium cation, withsodium and potassium being most preferred, and X is a halide, hydroxide,methylsulfate or acetate anion.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid onperhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include thesubstituted and unsubstituted benzoyl oxybenzene sulfonates, includingfor example benzoyl oxybenzene sulfonate: ##STR5##

Also suitable are the benzoylation products of sorbitol, glucose, andall saccharides with benzoylating agents, including for example:##STR6##

Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substitutedureas. Suitable imidazole type perbenzoic acid precursors includeN-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acylgroup-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides,the benzoyl tetraacyl peroxides, and the compound having the formula:##STR7##

Phthalic anhydride is another suitable perbenzoic acid precursorcompound herein: ##STR8##

Suitable N-acylated lactam perbenzoic acid precursors have the formula:##STR9## wherein n is from 0 to 8, preferably from 0 to 2, and R⁶ is abenzoyl group.

Perbenzoic Acid Derivative Precursors

Perbenzoic acid derivative precursors provide substituted perbenzoicacids on perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include anyof the herein disclosed perbenzoic precursors in which the benzoyl groupis substituted by essentially any non-positively charged (i.e.;non-cationic) functional group including, for example alkyl, hydroxy,alkoxy, halogen, amine, nitrosyl and amide groups.

A preferred class of substituted perbenzoic acid precursor compounds arethe amide substituted compounds of the following general formulae:##STR10## wherein R¹ is an aryl or alkaryl group with from 1 to 14carbon atoms, R² is an arylene, or alkarylene group containing from 1 to14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms and L can be essentially any leavinggroup. R¹ preferably contains from 6 to 12 carbon atoms. R² preferablycontains from 4 to 8 carbon atoms. R¹ may be aryl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourcedfrom either synthetic sources or natural sources including for example,tallow fat. Analogous structural variations are permissible for R². Thesubstitution can include alkyl, aryl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms intotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A-0170386.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting theperoxyacid part of a suitable peroxyacid precursor compound with apositively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methyl ammonium group.

Cationic peroxyacid precursors are typically present in the compositionsas a salt with a suitable anion, such as for example a halide ion or amethylsulfate ion.

The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative thereof, precursorcompound as described hereinbefore. Alternatively, the peroxyacidprecursor compound may be an alkyl percarboxylic acid precursor compoundor an amide substituted alkyl peroxyacid precursor as describedhereinafter.

Cationic peroxyacid precursors are described in U.S. Pat. Nos.4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852;5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292;and in JP 87-318,332.

Suitable cationic peroxyacid precursors include any of the ammonium oralkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates,N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoylperoxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzenesulfonate: ##STR11##

A preferred cationically substituted alkyl oxybenzene sulfonate has theformula: ##STR12##

Preferred cationic peroxyacid precursors of the N-acylated caprolactamclass include the trialkyl ammonium methylene benzoyl caprolactams,particularly trimethyl ammonium methylene benzoyl caprolactam: ##STR13##

Other preferred cationic peroxyacid precursors of the N-acylatedcaprolactam class include the trialkyl ammonium methylene alkylcaprolactam: ##STR14## where n is from 0 to 12, particularly from 1 to5.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethylammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N-,N,N¹ N¹ tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and penta acetyl glucose.

Amide Substituted Alkyl Peroxvacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are alsosuitable, including those of the following general formulae: ##STR15##wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. R¹ preferably contains from 6 to 12 carbon atoms. R²preferably contains from 4 to 8 carbon atoms. R¹ may be straight chainor branched alkyl containing branching, substitution, or both and may besourced from either synthetic sources or natural sources including forexample, tallow fat. Analogous structural variations are permissible forR². The substitution can include alkyl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms intotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A-0170386.

Benzoxazin Organic Peroxyacid Precursors

Also suitable are precursor compounds of the benzoxazin-type, asdisclosed for example in EP-A-332,294 and EP-A-482,807, particularlythose having the formula: ##STR16## including the substitutedbenzoxazins of the type ##STR17## wherein R₁ is H, alkyl, alkaryl, aryl,arylalkyl, and wherein R₂, R₃, R₄, and R₅ may be the same or differentsubstituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl,alkoxyl, amino, alkyl amino, COOR₆ (wherein R₆ is H or an alkyl group)and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is: ##STR18##Preformed Organic Peroxvacid

The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, apreformed organic peroxyacid, typically at a level of from 0.5% to 25%by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amidesubstituted compounds of the following general formulae: ##STR19##wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbonatoms, R² is an alkylene, arylene, and alkarylene group containing from1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms. R¹ preferably contains from 6 to 12carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R¹ may bestraight chain or branched alkyl, substituted aryl or alkylarylcontaining branching, substitution, or both and may be sourced fromeither synthetic sources or natural sources including for example,tallow fat. Analogous structural variations are permissible for R². Thesubstitution can include alkyl, aryl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms intotal. Amide substituted organic peroxyacid compounds of this type aredescribed in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides,especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, anddiperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organicperoxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylicacid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Inorganic Perhydrate Bleaches

The compositions in accord with the invention may include a secondhydrogen peroxide source, as a further oxygen-releasing bleach. Suitablehydrogen peroxide sources include other inorganic perhydrate salts.

The inorganic perhydrate salts are normally incorporated in the form ofthe sodium salt at a level of from 1% to 40% by weight, more preferablyfrom 2% to 30% by weight and most preferably from 5% to 25% by weight ofthe compositions.

Examples of other inorganic perhydrate salts include perborate,perphosphate, persulfate and persilicate salts. The inorganic perhydratesalts are normally the alkali metal salts. The inorganic perhydrate saltmay be included as the crystalline solid without additional protection.For certain perhydrate salts however, the preferred executions of suchgranular compositions utilize a coated form of the material whichprovides better storage stability for the perhydrate salt in thegranular product.

Sodium perborate can be in the form of the monohydrate of nominalformula NaBO₂ H₂ O₂ or the tetrahydrate NaBO₂ H₂ O₂.3H₂ O.

Potassium peroxymonopersulfate is another inorganic perhydrate salt ofutility in the compositions herein.

Metal-containing Bleach Catalyst

The bleach compositions described herein may additionally contain as apreferred component, a metal containing bleach catalyst. Preferably themetal containing bleach catalyst is a transition metal containing bleachcatalyst, more preferably a manganese or cobalt-containing bleachcatalyst.

A suitable type of bleach catalyst is a catalyst comprising a heavymetal cation of defined bleach catalytic activity, such as copper, ironcations, an auxiliary metal cation having little or no bleach catalyticactivity, such as zinc or aluminum cations, and a sequestrant havingdefined stability constants for the catalytic and auxiliary metalcations, particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Preferred types of bleach catalysts include the manganese-basedcomplexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No.5,244,594. Preferred examples of these catalysts include Mn^(IV) ₂(u-O)₃ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(PF₆)₂, Mn^(III) ₂(u-O)₁ (u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂,Mn^(IV) ₄ (u-O)₆ (1,4,7-triazacyclononane)₄ -(ClO₄)₂, Mn^(III) Mn^(IV) ₄(u-O)₁ (u-OAc)₂₋ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₃,and mixtures thereof. Others are described in European patentapplication publication no. 549,272. Other ligands suitable for useherein include 1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in the compositions herein may also beselected as appropriate for the present invention. For examples ofsuitable bleach catalysts see U.S. Pat. No. 4,246,612 and U.S. Pat. No.5,227,084. See also U.S. Pat. No. 5,194,416 which teaches mononuclearmanganese (IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃₋ (PF₆).

Still another type of bleach catalyst, as disclosed in U.S. Pat. No.5,114,606, is a water-soluble complex of manganese (III), and/or (IV)with a ligand which is a non-carboxylate polyhydroxy compound having atleast three consecutive C--OH groups. Preferred ligands includesorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol,meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. No. 5,114,611 teaches a bleach catalyst comprising a complexof transition metals, including Mn, Co, Fe, or Cu, with annon-(macro)-cyclic ligand. Said ligands are of the formula: ##STR20##wherein R¹, R², R³, and R⁴ can each be selected from H, substitutedalkyl and aryl groups such that each R¹ --N═C--R² and R³ --C═N--R⁴ forma five or six-membered ring. Said ring can further be substituted. B isa bridging group selected from O, S. CR⁵ R⁶, NR⁷ and C═O, wherein R⁵,R⁶, and R⁷ can each be H, alkyl, or aryl groups, including substitutedor unsubstituted groups. Preferred ligands include pyridine, pyridazine,pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.Optionally, said rings may be substituted with substituents such asalkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is theligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu,Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highlypreferred catalysts include Co(2,2'-bispyridylamine)Cl₂,Di(isothiocyanato)bispyridylamine-cobalt (II),trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)₂ O₂ClO₄, Bis-(2,2'-bispyridylamine) copper(II) perchlorate,tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentateand bi-N-dentate ligands, including N₄ Mn^(III) (u-O)₂ Mn^(IV) N₄)⁺ and[Bipy₂ Mn^(III) (u-O)₂ Mn^(IV) bipy₂ ]-(ClO₄)₃.

While the structures of the bleach-catalyzing manganese complexes of thepresent invention have not been elucidated, it may be speculated thatthey comprise chelates or other hydrated coordination complexes whichresult from the interaction of the carboxyl and nitrogen atoms of theligand with the manganese cation. Likewise, the oxidation state of themanganese cation during the catalytic process is not known withcertainty, and may be the (+II), (+III), (+IV) or (+V) valence state.Due to the ligands' possible six points of attachment to the manganesecation, it may be reasonably speculated that multi-nuclear speciesand/or "cage" structures may exist in the aqueous bleaching media.Whatever the form of the active Mn.ligand species which actually exists,it functions in an apparently catalytic manner to provide improvedbleaching performances on stubborn stains such as tea, ketchup, coffee,wine, juice, and the like.

Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Other preferred examples include cobalt (III) catalysts having theformula:

    Co[(NH.sub.3).sub.n M'.sub.m B'.sub.b T'.sub.t Q.sub.q P.sub.p ]Yy

wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5(preferably 4 or 5; most preferably 5); M' represents a monodentateligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably1); B' represents a bidentate ligand; b is an integer from 0 to 2; T'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand;q is 0 or 1; P is a pentadentate ligand; p is 0 or -1; andn+m+2b+3t+4q+5p=6; Y is one or more appropriately selected counteranionspresent in a number y, where y is an integer from 1 to 3 (preferably 2to 3; most preferably 2 when Y is a -1 charged anion), to obtain acharge-balanced salt, preferred Y are selected from the group consistingof chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, andcombinations thereof; and wherein further at least one of thecoordination sites attached to the cobalt is labile under automaticdishwashing use conditions and the remaining coordination sitesstabilize the cobalt under automatic dishwashing conditions such thatthe reduction potential for cobalt (III) to cobalt (II) under alkalineconditions is less than about 0.4 volts (preferably less than about 0.2volts) versus a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:

    [Co(NH.sub.3).sub.n (M').sub.m ]Y.sub.y

wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably5); M' is a labile coordinating moiety, preferably selected from thegroup consisting of chlorine, bromine, hydroxide, water, and (when m isgreater than 1) combinations thereof; m is an integer from 1 to 3(preferably 1 or 2; most preferably 1); m+n=6; and Y is an appropriatelyselected counteranion present in a number y, which is an integer from 1to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 chargedanion), to obtain a charge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobaltpentaamine chloride salts having the formula [Co(NH₃)₅ Cl]Y_(y), andespecially [Co(NH₃)₅ Cl]Cl₂.

More preferred are the present invention compositions which utilizecobalt (III) bleach catalysts having the formula:

    [Co(NH.sub.3).sub.n (M).sub.m (B).sub.b ]T.sub.y

wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5);M is one or more ligands coordinated to the cobalt by one site; m is 0,1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by twosites; b is 0 or 1 (preferably 0), and when b=0, then m+n=6, and whenb=1, then m=0 and n=4; and T is one or more appropriately selectedcounteranions present in a number y, where y is an integer to obtain acharge-balanced salt (preferably y is 1 to 3; most preferably 2 when Tis a -1 charged anion); and wherein further said catalyst has a basehydrolysis rate constant of less than 0.23 M⁻¹ s⁻¹ (25° C.).

Preferred T are selected from the group consisting of chloride, iodide,I₃ -, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate,carbonate, bromide, PF₆ -, BF₄ -, B(Ph)₄ -, phosphate, phosphite,silicate, tosylate, methanesulfonate, and combinations thereof.Optionally, T can be protonated if more than one anionic group exists inT, e.g., HPO₄ ² -, HCO₃ -, H₂ PO₄ -, etc. Further, T may be selectedfrom the group consisting of non-traditional inorganic anions such asanionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkylsulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionicpolymers (e.g., polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to, for example, F-, SO₄ -²,NCS-, SCN-, S₂ O₃ -², NH₃, PO₄ ³ -, and carboxylates (which preferablyare mono-carboxylates, but more than one carboxylate may be present inthe moiety as long as the binding to the cobalt is by only onecarboxylate per moiety, in which case the other carboxylate in the Mmoiety may be protonated or in its salt form). Optionally, M can beprotonated if more than one anionic group exists in M (e.g., HPO₄ ² -,HCO₃ -, H₂ PO₄ -, HOC(O)CH₂ C(O)O--, etc.) Preferred M moieties aresubstituted and unsubstituted C₁ -C₃₀ carboxylic acids having theformulas:

    RC(O)O--

wherein R is preferably selected from the group consisting of hydrogenand C₁ -C₃₀ (preferably C₁ -C₁₈) unsubstituted and substituted alkyl, C₆-C₃₀ (preferably C₆ -C₁₈) unsubstituted and substituted aryl, and C₃-C₃₀ (preferably C₅ -C₁₈) unsubstituted and substituted heteroaryl,wherein substituents are selected from the group consisting of --NR'₃,--NR'₄ ⁺, --C(O)OR', --OR', --C(O)NR'₂, wherein R' is selected from thegroup consisting of hydrogen and C₁ -C₆ moieties. Such substituted Rtherefore include the moieties --(CH₂)_(n) OH and --(CH₂)_(n) NR'₄ ⁺,wherein n is an integer from 1 to about 16, preferably from about 2 toabout 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein Ris selected from the group consisting of hydrogen, methyl, ethyl,propyl, straight or branched C₄ -C₁₂ alkyl, and benzyl. Most preferred Ris methyl. Preferred carboxylic acid M moieties include formic, benzoic,octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic,adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic,triflate, tartrate, stearic, butyric, citric, acrylic, aspartic,fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g.,oxalate, malonate, malic, succinate, maleate), picolinic acid, and alphaand beta amino acids (e.g., glycine, alanine, beta-alanine,phenylalanine).

Cobalt bleach catalysts useful herein are known, being described forexample along with their base hydrolysis rates, in M. L. Tobe, "BaseHydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.,(1983), 2, pages 1-94. For example, Table 1 at page 17, provides thebase hydrolysis rates (designated therein as k_(OH)) for cobaltpentaamine catalysts complexed with oxalate (k_(OH) =2.5×10⁻⁴ M⁻¹ s⁻¹(25° C.)), NCS- (k_(OH) =5.0×10⁻⁴ M⁻¹ s⁻¹ (25° C.)), formate (k_(OH)=5.8×10⁻⁴ M⁻¹ s⁻¹ (25° C.)), and acetate (k_(OH) =9.6×10⁻⁴ M⁻¹ s⁻¹ (25°C.)). The most preferred cobalt catalyst useful herein are cobaltpentaamine acetate salts having the formula [Co(NH₃)₅ OAc]T_(y), whereinOAc represents an acetate moiety, and especially cobalt pentaamineacetate chloride, [Co(NH₃)₅ OAc]Cl₂ ; as well as [Co(NH₃)₅ OAc](OAc)₂ ;[Co(NH₃)₅ OAc](PF₆)₂ ; [Co(NH₃)₅ OAc](SO₄); [Co-(NH₃)₅ OAc](BF₄)_(2;)and [Co(NH₃)₅ OAc](NO₃)₂ (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article hereinbefore and the referencescited therein, in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar.7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis andCharacterization of Inorganic Compounds, W. L. Jolly (Prentice-Hall;1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21,2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis,173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952); aswell as the synthesis examples provided hereinafter.

These catalysts may be coprocessed with adjunct materials so as toreduce the color impact if desired for the aesthetics of the product, orto be included in enzyme-containing particles as exemplifiedhereinafter, or the compositions may be manufactured to contain catalyst"speckles".

Amino Tricarboxylic Acid (ATCA)

The amino tricarboxylic acid (ATCA) is selected from the group havingthe general formula as shown below. ##STR21## where R₁, R₂ and R₃ are analkyl group or substituted alkyl group of chain length C1 to C4, and nis 0 or 1. X is an organic substitutent group, that is a substituenttypically encountered in organic compounds, but excluding X being ahydrogen substituent. X can thus for example be an alkyl, aryl, alkenylor alkaryl group optionally substituted by any functionality includingfor example, amino, hydroxyl, amide and ether functionalities. X mayalso be an organic functional group including for example an amine,hydroxyl, amide, ester or ether group. X is preferably an alkyl group,most preferably a methyl or ethyl group. ATCA is most preferably methylglycine diacetic acid, that is where R₁ =R₂ =a --CH₂ -- group, n is 0and X=CH₃.

ATCA can be present at levels of greater than 0.0001% by weight,preferably from 0.001% to 40% by weight, most preferably from 0.1% to15% by weight of detergent composition. The weight ratio of percarbonatebleach compound to ATCA is preferably from 500:1 to 1:1, more preferablyfrom 200:1 to 5:1, most preferably from 100:1 to 10:1.

ATCA acts as a cation complexing chelant. ATCA forms water-solublechelates with calcium, magnesium, lead, copper, zinc, cadmium, mercury,manganese, iron, aluminium and other cationic polyvalent ions. Thestability constant (measured as log K _(MeZ)) of ATCA-calcium chelate isgreater than 5.0, preferably greater then 6.0. The stability constant ofthe preferred ATCA compound, methyl glycine diacetic acid (MGDA) is 7.0.The stability constant, log K _(MeZ) is measured in a solution of ionicstrength of 0.1, at a temperature of 25° C. The figure of >5.0 forlogK_(MeZ) indicates that the ratio of the concentration of theundissociated [CaATCA⁻ ] to the dissociated complex [Ca²⁺ ][ATCA³⁻ ], is>10⁵ :1.

Optional Detergent Components

The bleaching compositions herein are preferably incorporated withindetergent compositions which may contain various components includingsurfactants, alkalinity sources, water-soluble builder compounds, limesoap dispersants, organic polymeric compounds including polymeric dyetransfer inhibiting agents, crystal growth inhibitors, heavy metal ionsequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, sudssuppressors, solvents, fabric softening agents, optical brighteners andhydrotropes.

Surfactant

A highly preferred component of the compositions used in this inventionis a surfactant system comprising surfactant selected from anionic,cationic, nonionic ampholytic and zwitterionic surfactants and mixturesthereof. Automatic dishwashing machine products should be low foaming incharacter and thus the foaming of the surfactant system must besuppressed or more preferably be low foaming, typically nonionic incharacter. The surfactant system is typically present at a level of from0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, mostpreferably from 1% to 5% by weight of the compositions.

A typical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. A list ofsuitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issuedto Murphy on Mar. 31, 1981. A listing of surfactants typically includedin automatic dishwashing detergent compositions is given for example, inEP-A-0414 549 and PCT Applications Nos. WO 93/08876 and WO 93/08874.

Nonionic Surfactant

Essentially any nonionic surfactants useful for detersive purposes canbe included in the compositions. Preferred, non-limiting classes ofuseful nonionic surfactants are listed below.

Nonionic Ethoxylated Alcohol Surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 1 to about 25 moles of ethylene oxide are suitable for useherein. The alkyl chain of the aliphatic alcohol can either be straightor branched, primary or secondary, and generally contains from 6 to 22carbon atoms. Particularly preferred are the condensation products ofalcohols having an alkyl group containing from 8 to 20 carbon atoms withfrom about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Nonionic Ethoxylated/propoxylated Fatty Alcohol Surfactant

The ethoxylated C₆ -C₁₈ fatty alcohols and C₆ -C₁₈ mixedethoxylated/propoxylated fatty alcohols are suitable surfactants for useherein, particularly where water soluble. Preferably the ethoxylatedfatty alcohols are the C₁₀ -C₁₈ ethoxylated fatty alcohols with a degreeof ethoxylation of from 3 to 50, most preferably these are the C₁₂ -C₁₈ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.Preferably the mixed ethoxylated/propoxylated fatty alcohols have analkyl chain length of from 10 to 18 carbon atoms, a degree ofethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to10.

Nonionic EO/PO Condensates with Propylene Glycol

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol aresuitable for use herein. The hydrophobic portion of these compoundspreferably has a molecular weight of from about 1500 to about 1800 andexhibits water insolubility. Examples of compounds of this type includecertain of the commercially-available Pluronic™ surfactants, marketed byBASF.

Nonionic EO Condensation Products with Propylene Oxide/ethylene DiamineAdducts

The condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylenediamine are suitablefor use herein. The hydrophobic moiety of these products consists of thereaction product of ethylenediamine and excess propylene oxide, andgenerally has a molecular weight of from about 2500 to about 3000.Examples of this type of nonionic surfactant include certain of thecommercially available Tetronic™ compounds, marketed by BASF.

Anionic Surfactant

Essentially any anionic surfactants useful for detersive purposes aresuitable. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate,carboxylate and sarcosinate surfactants. Anionic sulfate surfactants arepreferred.

Other anionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂ -C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆ -C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C₅ -C₁₇ acyl-N--(C₁ -C₄ alkyl) and --N--(C₁ -C₂hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharidessuch as the sulfates of alkylpolyglucoside (the nonionic nonsulfatedcompounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear andbranched primary C₁₀ -C₁₈ alkyl sulfates, more preferably the C₁₁ -C₁₅branched chain alkyl sulfates and the C₁₂ -C₁₄ linear chain alkylsulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₁₀ -C₁₈ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁ -C₁₈, mostpreferably C₁₁ -C₁₅ alkyl sulfate which has been ethoxylated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and alkyl ethoxysulfate surfactants. Suchmixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅ -C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂ primary or secondary alkane sulfonates, C₆ -C₂₄ olefin sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixturesthereof.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (`alkyl carboxyls`), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH₂CH₂ 0)_(x) CH₂ C00^(-M) ⁺ wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom 0 to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO--(CHR₁ --CHR₂ --O)--R₃ wherein R is a C₆ toC₁₈ alkyl group, x is from 1 to 25, R₁ and R₂ are selected from thegroup consisting of hydrogen, methyl acid radical, succinic acidradical, hydroxysuccinic acid radical, and mixtures thereof, and R₃ isselected from the group consisting of hydrogen, substituted orunsubstituted hydrocarbon having between 1 and 8 carbon atoms, andmixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certainsoaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R--CON (R¹) CH₂ COOM, wherein R is a C₅ -C₁₇ linear or branchedalkyl or alkenyl group, R¹ is a C₁ -C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Water-soluble Builder Compound

The compositions of the present invention may contain as a highlypreferred component a water-soluble builder compound, typically presentat a level of from 1% to 80% by weight, preferably from 10% to 70% byweight, most preferably from 20% to 60% by weight of the composition.

The compositions used in accord with this invention may optionallycontain an additional builder compound. Suitable water-soluble buildercompounds include the water soluble monomeric polycarboxylates, or theiracid forms, homo or copolymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxylic radicalsseparated from each other by not more that two carbon atoms, carbonates,bicarbonates, borates, phosphates, and mixtures thereof.

The carboxylate or polycarboxylate builder can be monomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates containing three carboxy groupsinclude, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivatives such as thecarboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, and theoxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylatesdescribed in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates,2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates,2,5-tetrahydrofuran-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpolycarboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acidor citrate/citric acid mixtures are also contemplated as useful buildercomponents.

Borate builders, as well as builders containing borate-forming materialsthat can produce borate under detergent storage or wash conditions canalso be used but are not preferred at wash conditions less that about50° C., especially less than about 40° C.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates, including sodium carbonate and sesqui-carbonate and mixturesthereof with ultra-fine calcium carbonate as disclosed in German PatentApplication No. 2,321,001 published on Nov. 15, 1973.

Specific examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammonium pyrophosphate,sodium and potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The detergent compositions of the present invention may contain apartially soluble or insoluble builder compound, typically present at alevel of from 1% to 80% by weight, preferably from 10% to 70% by weight,most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodiumaluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na_(z)[(AlO₂)_(z) (SiO₂)y]. xH₂ O wherein z and y are at least 6; the molarratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from7.5 to 276, more preferably from 10 to 264. The aluminosilicate materialare in hydrated form and are preferably crystalline, containing from 10%to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formula

    Na.sub.12 [AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]. xH.sub.2 O

wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆ [(AlO₂)₈₆ (SiO₂)₁₀₆ ]. 276 H₂ O.

Water-soluble Bismuth Compound

The compositions used in this invention may contain a water-solublebismuth compound, preferably present at a level of from 0.005% to 20%,more preferably from 0.01% to 5%, most preferably from 0.1% to 1% byweight of the compositions.

The water-soluble bismuth compound may be essentially any salt orcomplex of bismuth with essentially any inorganic or organic counteranion. Preferred inorganic bismuth salts are selected from the bismuthtrihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate andcitrate are preferred salts with an organic counter anion.

Water-soluble Sulfate Salt

The compositions may optionally contain a water-soluble sulfate salt,preferably present at a level of from 0.1% to 40%, more preferably from1% to 30%, most preferably from 5% to 25% by weight of the compositions.

The water-soluble sulfate salt may be essentially any salt of sulfatewith any counter cation. Preferred salts are selected from the sulfatesof the alkali and alkaline earth metals, particularly sodium sulfate.

Corrosion Inhibitor Compound

The compositions may contain corrosion inhibitors preferably selectedfrom organic silver coating agents, particularly paraffin,nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds,particularly Mn(II) salts of organic ligands.

Organic silver coating agents are described in PCT Publication No.WO94/16047 and copending UK Application No. UK 9413729.6.Nitrogen-containing corrosion inhibitor compounds are disclosed incopending European Application no. EP 93202095.1. Mn(II) compounds foruse in corrosion inhibition are described in copending UK ApplicationNo. 9418567.5.

Organic Silver Coating Agents

Organic silver coating agent may be incorporated at a level of from0.05% to 10%, preferably from 0.1% to 5% by weight of the totalcomposition.

The functional role of the silver coating agent is to form `in use` aprotective coating layer on any silverware components of the washload towhich the compositions of the invention are being applied. The silvercoating agent should hence have a high affinity for attachment to solidsilver surfaces, particularly when present in as a component of anaqueous washing and bleaching solution with which the solid silversurfaces are being treated.

Suitable organic silver coating agents herein include fatty esters ofmono- or polyhydric alcohols having from 1 to about 40 carbon atoms inthe hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- orpoly-carboxylic acids having from 1 to about 40 carbon atoms in thehydrocarbon chain. Suitable examples of monocarboxylic fatty acidsinclude behenic acid, stearic acid, oleic acid, palmitic acid, myristicacid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyricacid, Valerie acid, lactic acid, glycolic acid andβ,β'-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acidsinclude: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid,malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by mono-or polyhydric alcohols having from 1 to 40 carbon atoms in thehydrocarbon chain. Examples of suitable fatty alcohols include; behenyl,arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol,ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose,erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and/or fatty alcohol group of the fatty esteradjunct material have from 1 to 24 carbon atoms in the alkyl chain.

Preferred fatty esters herein are ethylene glycol, glycerol and sorbitanesters wherein the fatty acid portion of the ester normally comprises aspecies selected from behenic acid, stearic acid, oleic acid, palmiticacid or myristic acid.

The glycerol esters are also highly preferred. These are the mono-, di-or tri-esters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters for use herein include:stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate,oleyl dimaleate, and tallowyl proprionate. Fatty acid esters usefulherein include: xylitol monopalmitate, pentaerythritol monostearate,sucrose monostearate, glycerol monostearate, ethylene glycolmonostearate, sorbitan esters. Suitable sorbitan esters include sorbitanmonostearate, sorbitan palmitate, sorbitan monolaurate, sorbitanmonomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitandilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate,and also mixed tallowalkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate,glycerol monobehenate, and glycerol distearate are preferred glycerolesters herein.

Suitable organic silver coating agents include triglycerides, mono ordiglycerides, and wholly or partially hydrogenated derivatives thereof,and any mixtures thereof. Suitable sources of fatty acid esters includevegetable and fish oils and animal fats. Suitable vegetable oils includesoy bean oil, cotton seed oil, castor oil, olive oil, peanut oil,safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil andcorn oil.

Waxes, including microcrystalline waxes are suitable organic silvercoating agents herein. Preferred waxes have a melting point in the rangefrom about 35° C. to about 110° C. and comprise generally from 12 to 70carbon atoms. Preferred are petroleum waxes of the paraffin andmicrocrystalline type which are composed of long-chain saturatedhydrocarbon compounds.

Alginates and gelatin are suitable organic silver coating agents herein.

Dialkyl amine oxides such as C₁₂ -C₂₀ methylamine oxide, and dialkylquaternary ammonium compounds and salts, such as the C₁₂ -C₂₀methylammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymericmaterials. Polyvinylpyrrolidones with an average molecular weight offrom 12,000 to 700,000, polyethylene glycols (PEG) with an averagemolecular weight of from 600 to 10,000, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulosederivatives such as methylcellulose, carboxymethylcellulose andhydroxyethylcellulose are examples of such polymeric materials.

Certain perfume materials, particularly those demonstrating a highsubstantivity for metallic surfaces, are also useful as the organicsilver coating agents herein.

Polymeric soil release agents can also be used as an organic silvercoating agent.

Suitable polymeric soil release agents include those soil release agentshaving: (a) one or more nonionic hydrophile components consistingessentially of (i) polyoxyethylene segments with a degree ofpolymerization of at least 2, or (ii) oxypropylene or polyoxypropylenesegments with a degree of polymerization of from 2 to 10, wherein saidhydrophile segment does not encompass any oxypropylene unit unless it isbonded to adjacent moieties at each end by ether linkages, or (iii) amixture of oxyalkylene units comprising oxyethylene and from 1 to about30 oxypropylene units, said hydrophile segments preferably comprising atleast about 25% oxyethylene units and more preferably, especially forsuch components having about 20 to 30 oxypropylene units, at least about50% oxyethylene units; or (b) one or more hydrophobe componentscomprising (i) C₃ oxyalkylene terephthalate segments, wherein, if saidhydrophobe components also comprise oxyethylene terephthalate, the ratioof oxyethylene terephthalate:C₃ oxyalkylene terephthalate units is about2:1 or lower, (ii) C₄ -C₆ alkylene or oxy C₄ -C₆ alkylene segments, ormixtures therein, (iii) poly (vinyl ester) segments, preferablypolyvinyl acetate, having a degree of polymerization of at least 2, or(iv) C₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether substituents, ormixtures therein, wherein said substituents are present in the form ofC₁ -C₄ alkyl ether or C₄ hydroxyalkyl ether cellulose derivatives, ormixtures therein, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used,preferably from 3 to about 150, more preferably from 6 to about 100.Suitable oxy C₄ -C₆ alkylene hydrophobe segments include, but are notlimited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_(n) OCH₂ CH₂ O--, where M is sodium and n is an integer from 4-6,as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 toGosselink.

Polymeric soil release agents useful herein also include cellulosicderivatives such as hydroxyether cellulosic polymers, copolymeric blocksof ethylene terephthalate or propylene terephthalate with polyethyleneoxide or polypropylene oxide terephthalate, and the like. Such agentsare commercially available and include hydroxyethers of cellulose suchas METHOCEL (Dow). Cellulosic soil release agents for use herein alsoinclude those selected from the group consisting of C₁ -C₄ alkyl and C₄hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec. 28,1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.

Another suitable soil release agent is a copolymer having random blocksof ethylene terephthalate and polyethylene oxide (PEO) terephthalate.The molecular weight of this polymeric soil release agent is in therange of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadurissued Jul. 8, 1975.

Another suitable polymeric soil release agent is a polyester with repeatunits of ethylene terephthalate units contains 10-15% by weight ofethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000.

Another suitable polymeric soil release agent is a sulfonated product ofa substantially linear ester oligomer comprised of an oligomeric esterbackbone of terephthaloyl and oxyalkyleneoxy repeat units and terminalmoieties covalently attached to the backbone. These soil release agentsare described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 toJ. J. Scheibel and E. P. Gosselink. Other suitable polymeric soilrelease agents include the terephthalate polyesters of U.S. Pat. No.4,711,730, issued Dec. 8, 1987 to Gosselink et al, the anionicend-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26,1988 to Gosselink, and the block polyester oligomeric compounds of U.S.Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink. Other polymericsoil release agents also include the soil release agents of U.S. Pat.No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al, which disclosesanionic, especially sulfoarolyl, end-capped terephthalate esters.

Another soil release agent is an oligomer with repeat units ofterephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy andoxy-1,2-propylene units. The repeat units form the backbone of theoligomer and are preferably terminated with modified isethionateend-caps. A particularly preferred soil release agent of this typecomprises about one sulfoisophthaloyl unit, 5 terephthaloyl units,oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate.

A preferred organic silver coating agent is a paraffin oil, typically apredominantly branched aliphatic hydrocarbon having a number of carbonatoms in the range of from 20 to 50; preferred paraffin oil selectedfrom predominantly branched C₂₅₋₄₅ species with a ratio of cyclic tononcyclic hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1.A paraffin oil meeting these characteristics, having a ratio of cyclicto noncyclic hydrocarbons of about 32:68, is sold by Wintershall,Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen-containing Corrosion Inhibitor Compounds

Suitable nitrogen-containing corrosion inhibitor compounds includeimidazole and derivatives thereof such as benzimidazole, 2-heptadecylimidazole and those imidazole derivatives described in Czech Patent No.139, 279 and British Patent GB-A-1,137,741, which also discloses amethod for making imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibitor compounds, arepyrazole compounds and their derivatives, particularly those where thepyrazole is substituted in any of the 1, 3, 4 or 5 positions bysubstituents R₁, R₃, R₄ and R₅ where R₁ is any of H, CH₂ OH, CONH₃, orCOCH₃, R₃ and R₅ are any of C₁ -C₂₀ alkyl or hydroxyl, and R₄ is any ofH, NH₂ or NO₂.

Other suitable nitrogen-containing corrosion inhibitor compounds includebenzotriazole, 2-mercaptobenzothiazole,1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine,distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole,aminotetrazole and indazole.

Nitrogen-containing compounds such as amines, especially distearylamineand ammonium compounds such as ammonium chloride, ammonium bromide,ammonium sulphate or diammonium hydrogen citrate are also suitable.

Mn(II) Corrosion Inhibitor Compounds

The compositions may contain an Mn(II) corrosion inhibitor compound. TheMn(II) compound is preferably incorporated at a level of from 0.005% to5% by weight, more preferably from 0.01% to 1%, most preferably from0.02% to 0.4% by weight of the compositions. Preferably, the Mn(II)compound is incorporated at a level to provide from 0.1 ppm to 250 ppm,more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20ppm by weight of Mn(II) ions in any bleaching solution.

The Mn (II) compound may be an inorganic salt in anhydrous, or anyhydrated forms. Suitable salts include manganese sulphate, manganesecarbonate, manganese phosphate, manganese nitrate, manganese acetate andmanganese chloride. The Mn(II) compound may be a salt or complex of anorganic fatty acid such as manganese acetate or manganese stearate.

The Mn(II) compound may be a salt or complex of an organic ligand. Inone preferred aspect the organic ligand is a heavy metal ionsequestrant. In another preferred aspect the organic ligand is a crystalgrowth inhibitor.

Other Corrosion Inhibitor Compounds

Other suitable additional corrosion inhibitor compounds include,mercaptans and diols, especially mercaptans with 4 to 20 carbon atomsincluding lauryl mercaptan, thiophenol, thionapthol, thionalide andthioanthranol. Also suitable are saturated or unsaturated C₁₀ -C₂₀ fattyacids, or their salts, especially aluminium tristearate. The C₁₂ -C₂₀hydroxy fatty acids, or their salts, are also suitable. Phosphonatedoctadecane decane and other anti-oxidants such as betahydroxytoluene(BHT) are also suitable.

Copolymers of butadiene and maleic acid, particularly those suppliedunder the trade reference no. 07787 by Polysciences Inc have been foundto be of particular utility as corrosion inhibitor compounds.

Total Available Oxygen (AvO) Level

It has been found that, for optimal anti-silver tarnishing performance,the level of available oxygen in the present compositions, measured inunits of % available oxygen by weight of the composition, is preferablycontrolled; the level of available oxygen should hence preferably be inthe range from 0.3% to 2.5%, preferably from 0.5% to 1.7%, morepreferably from 0.6% to 1.5%, most preferably from 0.7% to 1.2%,measured according to the method described hereunder.

Rate of Release of AvO

The rate of release of available oxygen is preferably also controlled;the rate of release of available oxygen from the compositions hereinpreferably should be such that, when using the method describedhereinafter, the available oxygen is not completely released from thecomposition until after 3.5 minutes, preferably the available oxygen isreleased in a time interval of from 3.5 minutes to 10.0 minutes, morepreferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0minutes to 8.5 minutes.

Method for Measuring Level of Total Available Oxygen (AvO) and Rate ofRelease of AvO in a Detergent Composition

Method

1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, andthe stirrer speed is selected to ensure that the product is evenlydispersed through the solution.

2. The detergent composition (typically 8 g of product which has beensampled down from a bulk supply using a Pascal sampler), is added andsimultaneously a stop clock is started.

3. The temperature control should be adjusted so as to maintain aconstant temperature of 20° C. throughout the experiment.

4. Samples are taken from the detergent solution at 2 minute timeintervals for 20 minutes, starting after 1 minute, and are titrated bythe "titration procedure" described below to determine the level ofavailable oxygen at each point.

Titration Procedure

1. An aliquot from the detergent solution (above) and 2 ml sulphuricacid are added into a stirred beaker 2. Approximately 0.2 g ammoniummolybdate catalyst (tetra hydrate form) are added

3. 3 mls of 10% sodium iodide solution are added

4. Titration with sodium thiosulphate is conducted until the end point.The end point can be seen using either of two procedures. Firstprocedure consists simply in seeing the yellow iodine colour fading toclear. The second and preferred procedure consists of adding solublestarch when the yellow colour is becoming faint, turning the solutionblue. More thiosulphate is added until the end point is reached (bluestarch complex is decolourised).

The level of AvO, measured in units of % available oxygen by weight, forthe sample at each time interval corresponds to the amount of titreaccording to the following equation ##EQU1## AvO level is plotted versustime to determine the maximum level of AvO, and the rate of release ofAvO

Controlled Rate of Release--Means

A means may be provided for controlling the rate of release of oxygenbleach to the wash solution.

Means for controlling the rate of release of the bleach may provide forcontrolled release of peroxide species to the wash solution. Such meanscould, for example, include controlling the release of any inorganicperhydrate salt, acting as a hydrogen peroxide source, to the washsolution.

Suitable controlled release means can include coating any suitablecomponent with a coating designed to provide the controlled release. Thecoating may therefore, for example, comprise a poorly water solublematerial, or be a coating of sufficient thickness that the kinetics ofdissolution of the thick coating provide the controlled rate of release.

The coating material may be applied using various methods. Any coatingmaterial is typically present at a weight ratio of coating material tobleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.

Suitable coating materials include triglycerides (e.g. partially)hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono ordiglycerides, microcrystalline waxes, gelatin, cellulose, fatty acidsand any mixtures thereof.

Other suitable coating materials can comprise the alkali and alkalineearth metal sulphates, silicates and carbonates, including calciumcarbonate and silicas.

A preferred coating material, particularly for an inorganic perhydratesalt bleach source, comprises sodium silicate of SiO₂ :Na₂ O ratio from1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate,preferably applied at a level of from 2% to 10%, (normally from 3% to5%) of SiO₂ by weight of the inorganic perhydrate salt. Magnesiumsilicate can also be included in the coating.

Any inorganic salt coating materials may be combined with organic bindermaterials to provide composite inorganic salt/organic binder coatings.Suitable binders include the C₁₀ -C₂₀ alcohol ethoxylates containingfrom 5-100 moles of ethylene oxide per mole of alcohol and morepreferably the C₁₅ -C₂₀ primary alcohol ethoxylates containing from20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials.Polyvinylpyrrolidones with an average molecular weight of from 12,000 to700,000 and polyethylene glycols (PEG) with an average molecular weightof from 600 to 5×10⁶ preferably 1000 to 400,000 most preferably 1000 to10,000 are examples of such polymeric materials. Copolymers of maleicanhydride with ethylene, methylvinyl ether or methacrylic acid, themaleic anhydride constituting at least 20 mole percent of the polymerare further examples of polymeric materials useful as binder agents.These polymeric materials may be used as such or in combination withsolvents such as water, propylene glycol and the above mentioned C₁₀-C₂₀ alcohol ethoxylates containing from 5-100 moles of ethylene oxideper mole. Further examples of binders include the C₁₀ -C₂₀ mono- anddiglycerol ethers and also the C₁₀ -C₂₀ fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts are other examples of binders suitable for useherein.

One method for applying the coating material involves agglomeration.Preferred agglomeration processes include the use of any of the organicbinder materials described hereinabove. Any conventionalagglomerator/mixer may be used including, but not limited to pan, rotarydrum and vertical blender types. Molten coating compositions may also beapplied either by being poured onto, or spray atomized onto a moving bedof bleaching agent.

Other means of providing the required controlled release includemechanical means for altering the physical characteristics of the bleachto control its solubility and rate of release. Suitable protocols couldinclude compaction, mechanical injection, manual injection, andadjustment of the solubility of the bleach compound by selection ofparticle size of any particulate component.

Whilst the choice of particle size will depend both on the compositionof the particulate component, and the desire to meet the desiredcontrolled release kinetics, it is desirable that the particle sizeshould be more than 500 micrometers, preferably having an averageparticle diameter of from 800 to 1200 micrometers.

Additional protocols for providing the means of controlled releaseinclude the suitable choice of any other components of the detergentcomposition matrix such that when the composition is introduced to thewash solution the ionic strength environment therein provided enablesthe required controlled release kinetics to be achieved.

Alkalinity System

The compositions preferably contain an alkalinity system containingsodium silicate having an SiO₂ :Na₂ O ratio of from 1.8 to 3.0,preferably from 1.8 to 2.4, most preferably 2.0, present preferably at alevel of less than 20%, preferably from 1% to 15%, most preferably from3% to 12% by weight of SiO₂. The alkali metal silicate may be in theform of either the anhydrous salt or a hydrated salt.

The alkalinity system also preferably contains sodium metasilicate,present at a level of at least 0.4% SiO₂ by weight. Sodium metasilicatehas a nominal SiO₂ :Na₂ O ratio of 1.0. The weight ratio of said sodiumsilicate to said sodium metasilicate, measured as SiO₂, is preferablyfrom 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably from10:1 to 5:2.

Heavy Metal Ion Sequestrant

The detergent compositions of the invention preferably contain as anoptional component a heavy metal ion sequestrant. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate) heavy metal ions. These components may also have calcium andmagnesium chelation capacity, but preferentially they show selectivityto binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25%to 7.5% and most preferably from 0.5% to 5% by weight of thecompositions.

Heavy metal ion sequestrants, which are acidic in nature, having forexample phosphonic acid or carboxylic acid functionalities, may bepresent either in their acid form or as a complex/salt with a suitablecounter cation such as an alkali or alkaline metal ion, ammonium, orsubstituted ammonium ion, or any mixtures thereof. Preferably anysalts/complexes are water soluble. The molar ratio of said countercation to the heavy metal ion sequestrant is preferably at least 1:1.

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates. Preferred among the above species are diethylene triaminepenta (methylene phosphonate), ethylene diamine tri (methylenephosphonate) hexamethylene diamine tetra (methylene phosphonate) andhydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,ethylenediamine disuccinic acid, ethylenediamine diglutaric acid,2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) orthe alkali metal, alkaline earth metal, ammonium, or substitutedammonium salts thereof, or mixtures thereof. Preferred EDDS compoundsare the free acid form and the sodium or magnesium salt or complexthereof.

Crystal Growth Inhibitor Component

The detergent compositions preferably contain a crystal growth inhibitorcomponent, preferably an organodiphosphonic acid component, incorporatedpreferably at a level of from 0.01% to 5%, more preferably from 0.1% to2% by weight of the compositions.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrant components.

The organo diphosphonic acid is preferably a C₁ -C₄ diphosphonic acid,more preferably a C₂ diphosphonic acid, such as ethylene diphosphonicacid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP)and may be present in partially or fully ionized form, particularly as asalt or complex.

Enzyme

Another optional ingredient useful in the compositions is one or moreenzymes. Preferred enzymatic materials include the commerciallyavailable lipases, amylases, neutral and alkaline proteases, esterases,cellulases, pectinases, lactases and peroxidases conventionallyincorporated into detergent compositions. Suitable enzymes are discussedin U.S. Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, and Esperaseby Novo Industries A/S (Denmark), those sold under the tradenameMaxatase, Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Protease enzyme may be incorporated into thecompositions in accordance with the invention at a level of from 0.0001%to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from aspecial strain of B licheniformis, described in more detail inGB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades,and those sold under the tradename Termamyl and BAN by Novo IndustriesA/S. Amylase enzyme may be incorporated into the composition inaccordance with the invention at a level of from 0.0001% to 2% activeenzyme by weight of the composition.

Lipolytic enzyme (lipase) may be present at levels of active lipolyticenzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% byweight, most preferably from 0.001% to 0.5% by weight of thecompositions. The lipase may be fungal or bacterial in origin. Lipasefrom chemically or genetically modified mutants of these strains arealso useful herein. A preferred lipase is described in Granted EuropeanPatent, EP-B-0218272.

An especially preferred lipase herein is obtained by cloning the genefrom Humicola lanuginosa and expressing the gene in Aspergillus oryza,as host, as described in European Patent Application, EP-A-0258 068,which is commercially available from Novo Industries A/S, Bagsvaerd,Denmark, under the trade name Lipolase. This lipase is also described inU.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Enzyme Stabilizing System

Preferred enzyme-containing compositions herein may comprise from about0.001% to about 10%, preferably from about 0.005% to about 8%, mostpreferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such stabilizingsystems can comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acid, boronic acid, chlorine bleach scavengers andmixtures thereof. Such stabilizing systems can also comprise reversibleenzyme inhibitors, such as reversible protease inhibitors.

Organic Polymeric Compound

Organic polymeric compounds may be added as preferred components of thecompositions in accord with the invention. By organic polymeric compoundit is meant essentially any polymeric organic compound commonly used asdispersants, and anti-redeposition and soil suspension agents indetergent compositions. Organic polymer compounds, however, have notbeen previously described as soil release agents in dishwashing.

Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.1% to 30%, preferablyfrom 0.5% to 15%, most preferably from 1% to 10% by weight of thecompositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylates of molecular weight 2000-10000 and their copolymerswith any suitable other monomer units including modified acrylic,fumaric, maleic, itaconic, aconitic, mesaconic, citraconic andmethylenemalonic acid or their salts, maleic anhydride, acrylamide,alkylene, vinylmethyl ether, styrene and any mixtures thereof. Preferredare the copolymers of acrylic acid and maleic anhydride having amolecular weight of from 20,000 to 100,000.

Preferred commercially available acrylic acid containing polymers havinga molecular weight below 15,000 include those sold under the tradenameSokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and thosesold under the tradename Acusol 45N by Rohm and Haas.

Preferred acrylic acid containing copolymers include those which containas monomer units: a) from 90% to 10%, preferably from 80% to 20% byweight acrylic acid or its salts and b) from 10% to 90%, preferably from20% to 80% by weight of a substituted acrylic monomer or its saltshaving the general formula --[CR₂ --CR₁ (CO--O--R₃)]-- wherein at leastone of the substituents R₁, R₂ or R₃, preferably R₁ or R₂ is a 1 to 4carbon alkyl or hydroxyalkyl group, R₁ or R₂ can be a hydrogen and R₃can be a hydrogen or alkali metal salt. Most preferred is a substitutedacrylic monomer wherein R₁ is methyl, R₂ is hydrogen (i.e. a methacrylicacid monomer). The most preferred copolymer of this type has a molecularweight of 3500 and contains 60% to 80% by weight of acrylic acid and 40%to 20% by weight of methacrylic acid.

The polyamino compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-A-305282, EP-A-305283 andEP-A-351629.

Clay Softening System

The detergent compositions may contain a clay softening systemcomprising a clay mineral compound and optionally a clay flocculatingagent.

The clay mineral compound is preferably a smectite clay compound.Smectite clays are disclosed in the U.S. Pat. Nos. 3,862,058, 3,948,790,3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 andEP-A-313,146 in the name of the Procter and Gamble Company describesuitable organic polymeric clay flocculating agents.

Lime Soap Dispersant Compound

The compositions of the invention may contain a lime soap dispersantcompound, preferably present at a level of from 0.1% to 40% by weight,more preferably 1% to 20% by weight, most preferably from 2% to 10% byweight of the compositions.

A lime soap dispersant is a material that prevents the precipitation ofalkali metal, ammonium or amine salts of fatty acids by calcium ormagnesium ions. Preferred lime soap dispersant compounds are disclosedin PCT Application No. W093/08877.

Suds Suppressing System

The compositions of the invention, when formulated for use in machinewashing compositions, preferably comprise a suds suppressing systempresent at a level of from 0.01% to 15%, preferably from 0.05% to 10%,most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds, 2-alkyl and alcanol antifoam compounds. Preferredsuds suppressing systems and antifoam compounds are disclosed in PCTApplication No. W093/08876 and copending European Application No.93870132.3.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein may also comprise from 0.01% to 10%, preferablyfrom 0.05% to 0.5% by weight of polymeric dye transfer inhibitingagents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

Optical Brightener

The detergent compositions herein also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula: ##STR22## wherein R₁ is selected from anilino,N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected fromN-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloroand amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation.

Tinopal-UNPA-GX is the preferred hydrophilic optical brightener usefulin the detergent compositions herein.

When in the above formula, R₁ is anilino, R2 isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic Fabric Softening Agents

Cationic fabric softening agents can also be incorporated intocompositions in accordance with the present invention. Suitable cationicfabric softening agents include the water insoluble tertiary amines ordilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0011 340.

Cationic fabric softening agents are typically incorporated at totallevels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, colours and filler salts, with sodiumsulfate being a preferred filler salt.

pH of the Compositions

The detergent compositions used in the present invention are preferablynot formulated to have an unduly high pH, in preference having a pHmeasured as a 1% solution in distilled water of from 8.0 to 12.5, morepreferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

Form of the Compositions

The detergent compositions used in this invention can be formulated inany desirable form such as powders, granulates, pastes, liquids, gelsand tablets, granular and tablet forms being preferred.

The bulk density of the granular detergent compositions in accordancewith the present invention is typically of at least 650 g/liter, moreusually at least 700 g/litre and more preferably from 800 g/liter to1200 g/liter.

The particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.4 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

Compacted solids may be manufactured using any suitable compactingprocess, such as tabletting, briquetting or extrusion, preferablytabletting. Preferably tablets are manufactured using a standard rotarytabletting press using compression forces of from 5 to 13 KN/cm², morepreferably from 5 to 11 KN/cm² so that the compacted solid has a minimumhardness of 176N to 275N, preferably from 195N to 245N, measured by aC100 hardness test as supplied by I. Holland instruments. This processmay be used to prepare homogeneous or layered tablets of any size orshape. Preferably tablets are symmetrical to ensure the uniformdissolution of the tablet in the wash solution.

According to the present invention the compacted solid form detergentcomposition may find utility in all types of automatic dish- and laundrywashing machines including industrial and domestic machines.

Generally, if the compositions are in liquid form the liquid should bethixotropic (ie; exhibit high viscosity when subjected to low stress andlower viscosity when subjected to high stress), or at least have veryhigh viscosity, for example, of from 1,000 to 10,000,000 centipoise.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalised high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents;

GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 andEP-A-0288346. An article by J. Bland published in Manufacturing Chemist,November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the "granulette". Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss in a spoked wheelconfiguration, or a similar structure in which the walls have a helicalform.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

EXAMPLES

Abbreviations Used in Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

    ______________________________________                                        LAS         Sodium linear C.sub.12 alkyl benzene sulfonate                    TAS         Sodium tallow alkyl sulfate                                       C45AS       Sodium C.sub.14 --C.sub.15 linear alkyl sulfate                   CxyEzS      Sodium C.sub.1x --C.sub.1y branched alkyl sulfate                             condensed with z moles of ethylene oxide                          C45E7       A C.sub.14-15 predominantly linear primary                                    alcohol condensed with an average of 7 moles                                  of ethylene oxide                                                 C25E3       A C.sub.14-15 branched primary alcohol condensed                              with an average of 3 moles of ethylene oxide                      C25E5       A C.sub.12-15 branched primary alcohol condensed                              with an average of 5 moles of ethylene oxide                      CEQ         R.sub.1 COOCH.sub.2 CH.sub.2.N.sup.+ (CH.sub.3).sub.3 With                    R.sub.1 = C.sub.11 --C.sub.13                                     QAS         R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH with                     R.sub.2 = C.sub.12 --C.sub.14                                     Soap        Sodium linear alkyl carboxylate derived from                                  an 80/20 mixture of tallow and coconut oils                       TFAA        C.sub.16 --C.sub.18 alkyl N-methyl glucamide                      TPKFA       C.sub.12 --C.sub.14 topped whole cut fatty acids                  Zeolite A   Hydrated Sodium Aluminosilicate of formula                                    Na.sub.12 (A10.sub.2 SiO.sub.2).sub.12.27H.sub.2 O having a                   primary                                                                       particle size in the range from 0.1 to                                        10 micrometers                                                    Zeolite MAP Hydrated sodium aluminosilicate MAP having                                    a silicon to aluminium ratio of 1.07:1.                           NaSKS-6     Crystalline layered silicate of formula                                       δ-Na.sub.2 Si.sub.2 O.sub.5                                 Citric Acid Anhydrous citric acid                                             Bicarbonate Anhydrous sodium bicarbonate with a particle                                  size distribution between 400 μm and 1200 μm                MA/AA       Copolymer of 1:4 maleic/acrylic acid, average                                 molecular weight about 70,000                                     CMC         Sodium carboxymethyl cellulose                                    Alcalase    Proteolytic enzyme of activity 3AU/g sold by                                  NOVO Industries A/S                                               Cellulase   Cellulytic enzyme of activity 1000 CEVU/g                                     sold by NOVO Industries A/S under the                                         tradename Carezyme                                                Lipase      Lipolytic enzyme of activity 100 kLU/g sold by                                NOVO Industries A/S under the tradename                                       Lipolase                                                          Endolase    Endoglucase enzyme of activity 3000 CEVU/g                                    sold by NOVO Industries A/S                                       Photoactivated bleach                                                                     Sulfonated Zinc Phythlocyanine encapsulated in                                dextrin soluble polymer                                           Brightener 1                                                                              Disodium 4,4'-bis(2-sulphostyryl)biphenyl                         Brightener 2                                                                              Disodium 4,4'-bis(4-anilino-6-morpholino-                                     1.3.5-triazin-2-yl)amino) stilbene-2:2'-                                      disulfonate                                                       PVNO        Polyvinylpyridine N-oxide                                         PVPVI       Copolymer of polyvinylpyrolidone and                                          vinylimidazole                                                    SRP 1       Sulfobenzoyl end capped esters with                                           oxyethylene oxy and terephtaloyl backbone                         SRP 2       Diethoxylated poly (1,2 propylene terephtlate)                                short block polymer                                               Silicone antifoam                                                                         Polydimethylsiloxane foam controller with                                     siloxane-oxyalkylene copolymer as dispersing                                  agent with a ratio of said form controller to                                 said dispersing agent of 10:1 to 100:1                            NOBS        Nonanoyloxybenzene sulfonate in the form of                                   the sodium salt                                                   STPP        Sodium tripolyphosphate                                           MGDA        Methyl Glycine Diacetic acid                                      Citrate     Tri-sodium citrate dihydrate                                      Carbonate   Anhydrous sodium carbonate                                        Silicate    Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O                              ratio = 2.0)                                                                  Sodium metasilicate (SiO.sub.2 :Na.sub.2 O ratio = 1.0)           Metasilicate                                                                  PB1         Anhydrous sodium perborate monohydrate                            PB4         Sodium perborate tetrahydrate of nominal                                      formula NaBO.sub.2.3H.sub.2 O.H.sub.2 O.sub.2                     Percarbonate                                                                              Anhydrous sodium percarbonate of nominal                                      formula 2.Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2                      Mn Catalyst Mn.sup.IV.sub.2 (m-O).sub.3 (1,4,7-trimethyl-1,4,7-                           triazacyclononane).sub.2 -(PF.sub.6).sub.2 as described in                    U.S. Pat. Nos. 5 246 621 and 5 244 594.                           Nonionic    C.sub.13 --C.sub.15 mixed ethoxylated/propoxylated fatty                      alcohol with an average degree of ethoxylation                                of 3.8 and an average degree of propoxylation                                 of 4.5 sold under the tradename Plurafac                                      LF404 by BASF GmbH (low foaming)                                  TAED        Tetraacetyl ethylene diamine                                      HEDP        Ethane 1-hydroxy-1,1-diphosphonic acid                            DETPMP      Diethyltriamine penta (methylene)                                             phosphonate, marketed by monsanto under the                                   tradename Dequest 2060                                            PAAC        Pentaamine acetate cobalt (III) salt                              BzP         Benzoyl Peroxide                                                  Paraffin    Paraffin oil sold under the tradename Winog 70                                by Wintershall.                                                   Protease    Proteolytic enzyme of activity 4KNPU/g sold                                   under the tradename Savinase by Novo                                          Industries A/S                                                    Amylase     Amylolytic enzyme of activity 60KNU/g sold                                    under tradename Termamyl 60T by Novo                                          Industries A/S                                                    BTA         Benzotriazole                                                     Bismuth nitrate                                                                           Bismuth nitrate salt                                              PA30        Polyacrylic acid of average molecular weight                                  approximately 8,000                                               Terpolymer  Terpolymer of average molecular weight                                        approx. 7,000, comprising                                                     acrylic:maleic:ethylacrylic acid monomer units                                at a weight ratio of 60:20:20                                     480N        Random copolymer of 3:7 acrylic/methacrylic                                   acid, average molecular weight about 3,500                        Sulphate    Anhydrous sodium sulphate.                                        NaDCC       Sodium dichloroisocyanurate                                       KOH         100% active solution of Potassium Hydroxide                       BSA         Amylotic enzyme sold under the tradename                                      LE17 by Novo Industries A/S (approx 1%                                        enzyme activity)                                                  pH          Measured as a 1% solution in distilled water at                               20° C.                                                     ______________________________________                                    

In the following examples all levels are quoted as % by weight of thecomposition:

Example 1

The following compact high density (0.96 Kg/l) dishwashing detergentcompositions A to F were prepared:

    ______________________________________                                                A     B       C       D     E     F                                   ______________________________________                                        STPP      24.80   24.80   25.00 28.39 28.50 20.00                             Citrate   --       --     --    --    10.00 10.00                             Carbonate --      --      17.50 17.50 --    --                                MGDA      --      2.50    2.00  2.00  3.00  2.00                              Silicate  20.36   20.36   14.81 14.81 14.81 --                                Metasilicate                                                                            2.50    2.50    2.50  --    --    --                                PB1       --      --      2.00  --    3.00  --                                Percarbonate                                                                            7.00    4.00    5.78  10.00 7.65  6.70                              Non-ionic 1.50    1.50    2.00  1.50  2.00  2.60                              TAED      2.39    2.39    2.39  --    --    4.00                              HEDP      0.46    0.46    1.00  --    0.83  --                                DETPMP    --      --      0.65  --    --    --                                PAAC      --      --      --    0.20  --    --                                BzP       --      --      --    4.44  --    --                                Paraffin  0.50    0.50    0.50  0.50  --    0.20                              Protease  2.20    2.20    2.20  2.20  2.00  0.50                              Amylase   1.50    1.50    1.20  1.50  1.00  1.10                              BTA       0.30    0.30    0.30  0.30  --    --                                Bismuth Nitrate                                                                         --      --      0.30  --    --    --                                PA30      --      --      --    --    --    --                                Terpolymer                                                                              --      --      --    4.00  --    --                                480N      2.77    2.77    6.00  --    6.67  --                                Sulphate  8.44    8.44    20.77 --    23.24 1.00                              Misc inc moisture                                                             to balance                                                                    pH (1% solution)                                                                        10.90   10.90   11.00 10.80 10.90 9.60                              ______________________________________                                    

Example 2

The following granular dishwashing detergent compositions examples G toL of bulk density 1.02 Kg/L were prepared in accord with the invention:

    ______________________________________                                                G     H       I       J     K     L                                   ______________________________________                                        STPP      30.00   30.00   30.00 27.90 34.50 26.70                             Carbonate 30.50   23.50   30.50 23.00 30.50 2.80                              MGDA      --       2.00   2.00  5.00  5.00  2.00                              Silicate  7.40    7.40    7.40  12.00 8.00  18.34                             PB1       --      --      --    --    4.40  --                                Percarbonate                                                                            6.00    6.00    6.00  2.00  2.00  1.50                              Nonionic  0.75    0.75    0.75  1.90  1.20  0.50                              TAED      1.00    1.00    --    --    1.00  --                                PAAC      --      --      0.004 --    --    --                                BzP       --      1.40    --    --    --    --                                Paraffin  0.25    0.25    0.25  --    --    --                                Protease  1.10    1.10    1.10  --    2.20  --                                Amylase   0.38    0.38    0.38  --    0.80  --                                BTA       0.15    --      0.15  --    --    --                                Sulphate  23.90   21.90   21.90 26.40 12.40 --                                Misc inc moisture                                                             to balance                                                                    pH (1% solution)                                                                        10.80   10.80   10.80 10.70 10.70 12.30                             ______________________________________                                    

Example 3

The following detergent composition tablets in accord with the presentinvention of 25 g weight were prepared by compression of a granulardishwashing detergent composition at a pressure of 13 KN/cm² using astandard 12 head rotary press:

    ______________________________________                                                  M          N       O                                                ______________________________________                                        STPP        45.00        38.80   32.50                                        Citrate     --            --     15.00                                        Carbonate   --           5.00    --                                           MGDA        --           4.00    2.00                                         Silicate    26.40        14.80   25.00                                        Protease    1.76         2.20    0.60                                         Amylase     1.20         --      0.60                                         PB1         1.56         --      --                                           Percarbonate                                                                              6.92         9.98    13.40                                        Nonionic    1.20         2.00    1.10                                         TAED        4.33         2.39    0.80                                         HEDP        0.67         0.67    --                                           DETPMP      0.65         --      --                                           Paraffin    0.42         0.50    --                                           BTA         0.24         0.30    --                                           PA30        3.2          --      --                                           Sulphate    25.05        12.70   1.20                                         Misc inc moisture                                                             to balance                                                                    pH (1% solution)                                                                          10.60        10.60   11.00                                        ______________________________________                                    

Example 4

The following liquid detergent compositions in accord with the presentinvention P to Q, of density 1.40 Kg/L were prepared:

    ______________________________________                                                       P     Q                                                        ______________________________________                                        STPP             31.30   18.00                                                Carbonate        2.70    2.00                                                 MGDA             2.00    2.00                                                 Silicate         --      4.40                                                 Percarbonate     5.00    6.40                                                 Nonionic         2.50    1.00                                                 Paraffin         2.20    --                                                   Protease         0.60    0.50                                                 Amylase          0.80    0.40                                                 480N             0.50    4.00                                                 KOH              --      6.00                                                 Sulphate         1.60    --                                                   Misc inc moisture                                                             to balance                                                                    pH (1% solution) 9.10    10.00                                                ______________________________________                                    

Example 5

The following granular laundry detergent compositions A' to C' of bulkdensity 750 g/liter were prepared in accord with the invention:

    ______________________________________                                                  A'         B'      C'                                               ______________________________________                                        LAS         5.25         5.61    4.76                                         TAS         1.25         1.86    1.57                                         C45AS       --           2.24    3.89                                         C25AE3S     --           0.76    1.18                                         C45E7       3.25         --      5.0                                          C25E3       --           5.5     --                                           CEQ         0.8          2.0     2.0                                          STPP        19.7         19.5    19.5                                         MGDA        0.2          0.3     10.0                                         Zeolite A   --           --      19.5                                         Zeolite MAP --           19.5    --                                           NaSKS-6/citric                                                                            --           10.6    10.6                                         acid (79:21)                                                                  Carbonate   6.1          21.4    21.4                                         Bicarbonate --           2.0     2.0                                          Silicate    6.8          --      --                                           Sodium sulfate                                                                            39.8         --      14.3                                         Percarbonate                                                                              7.0          14.7    14.0                                         Mn Catalyst 0.3          --      0.1                                          TAED        0.5          3.1     --                                           DETPMP      0.25         0.2     0.2                                          HEDP        --           0.3     0.3                                          Protease    0.26         0.85    0.85                                         Lipase      0.15         0.15    0.15                                         Cellulase   0.28         0.28    0.28                                         Amylase     0.1          0.1     0.1                                          MA/AA       0.8          1.6     1.6                                          CMC         0.2          0.4     0.4                                          Photoactivated                                                                            15 ppm       27 ppm  27 ppm                                       bleach (ppm)                                                                  Brightener 1                                                                              0.08         0.19    0.19                                         Brightener 2                                                                              --           0.04    0.04                                         Perfume     0.3          0.3     0.3                                          Silicone antifoam                                                                         0.5          2.4     2.4                                          Minors/misc                                                                   to 100%                                                                       ______________________________________                                    

Example 6

The following detergent formulations, according to the present inventionwere prepared:

    ______________________________________                                                   D'        E'      F'                                               ______________________________________                                        Blown Powder                                                                  STPP         24.0        --      24.0                                         Zeolite A    --          24.0    --                                           MGDA         0.1         0.5     2.0                                          C45AS        9.0         6.0     13.0                                         MA/AA        2.0         4.0     2.0                                          LAS          6.0         8.0     11.0                                         TAS          2.0         --      --                                           Silicate     7.0         3.0     3.0                                          CMC          1.0         1.0     0.5                                          Brightener 2 0.2         0.2     0.2                                          Soap         1.0         1.0     1.0                                          DTPMP        0.4         0.4     0.2                                          Spray On                                                                      C45E7        2.5         2.5     2.0                                          C25E3        2.5         2.5     2.0                                          Silicone antifoam                                                                          0.3         0.3     0.3                                          Perfume      0.3         0.3     0.3                                          Dry additives                                                                 Carbonate    6.0         13.0    15.0                                         PB4          3.0         4.0     --                                           Percarbonate 6.0         6.0     7.0                                          Mn Catalyst  --          0.3     --                                           TAED         3.0         3.0     1.0                                          Photoactivated                                                                             0.02        0.02    0.02                                         bleach                                                                        Protease     1.0         1.0     1.0                                          Lipase       0.4         0.4     0.4                                          Amylase      0.25        0.30    0.15                                         Dry mixed    3.0         3.0     5.0                                          sodium sulfate                                                                Balance (Moisture                                                                          100.0       100.0   100.0                                        & Miscellaneous)                                                              Density (g/liter)                                                                          630         670     670                                          ______________________________________                                    

Example 7

The following nil bleach-containing detergent formulations of particularuse in the washing of colored clothing, according to the presentinvention were prepared:

    ______________________________________                                                        G'    H'                                                      ______________________________________                                        Blown Powder                                                                  STPP              15.0    15.0                                                MGDA              0.2     2.0                                                 Sodium sulfate    0.0     5.0                                                 LAS               3.0     3.0                                                 DTPMP             0.4     0.5                                                 CMC               0.4     0.4                                                 MA/AA             4.0     4.0                                                 Agglomerates                                                                  C45AS             --       --                                                 LAS               6.0     5.0                                                 TAS               3.0     2.0                                                 Silicate          4.0     4.0                                                 Zeolite A         10.0    15.0                                                CMC               --      --                                                  MA/AA             --      --                                                  Carbonate         9.0     7.0                                                 Spray On                                                                      Perfume           0.3     0.3                                                 C45E7             4.0     4.0                                                 C25E3             2.0     2.0                                                 Dry additives                                                                 MA/AA             --      --                                                  NaSKS-6           --      --                                                  Citrate           10.0    --                                                  Bicarbonate       7.0     3.0                                                 Carbonate         8.0     5.0                                                 Percarbonate      10.00   14.00                                               Mn Catalyst       0.1     0.1                                                 PVPVI/PVNO        0.5     0.5                                                 Alcalase          0.5     0.3                                                 Lipase            0.4     0.4                                                 Amylase           0.6     0.6                                                 Cellulase         0.6     0.6                                                 Silicone antifoam 5.0     5.0                                                 Dry additives                                                                 Sodium sulfate    0.0     9.0                                                 Balance (Moisture 100.0   100.0                                               and Miscellaneous)                                                            Density (g/liter) 700     700                                                 ______________________________________                                    

Example 8

The following detergent formulations, according to the present inventionwere prepared:

    ______________________________________                                                   I'    J'        K'      L'                                         ______________________________________                                        LAS          20.0    14.0      24.0  22.0                                     QAS          0.7     1.0       --    0.7                                      TFAA         --      1.0       --    --                                       C25E5/C45E7  --      2.0       --    0.5                                      C45E3S       --      2.5       --    --                                       STPP         30.0    18.0      30.0  22.0                                     Silicate     9.0     5.0       10.0  8.0                                      Carbonate    13.0    7.5       --    5.0                                      MGDA         2.0     2.0       2.0   2.0                                      Bicarbonate  --      7.5       --    --                                       DTPMP        0.7     1.0       --    --                                       SRP 1        0.3     0.2       --    0.1                                      MA/AA        2.0     1.5       2.0   1.0                                      CMC          0.8     0.4       0.4   0.2                                      Protease     0.8     1.0       0.5   0.5                                      Amylase      0.8     0.4       --    0.25                                     Lipase       0.2     0.1       0.2   0.1                                      Cellulase    0.15    0.05      --    --                                       Photoactivated                                                                             70 ppm  45 ppm    --    10 ppm                                   bleach (ppm)                                                                  Brightener 1 0.2     0.2       0.08  0.2                                      Percarbonate 8.0     4.0       7.65  4.76                                     NOBS         2.0     1.0       --    --                                       Balance      100     100       100   100                                      (Moisture and                                                                 Miscellaneous)                                                                ______________________________________                                    

Example 9

The following detergent formulations, according to the present inventionwere prepared:

    ______________________________________                                                   M'        N'      O'                                               ______________________________________                                        Blown Powder                                                                  STPP         30.0        22.0    6.0                                          MGDA         2.0         2.0     2.0                                          Sodium sulfate                                                                             19.0        5.0     7.0                                          MA/AA        3.0         3.0     6.0                                          LAS          14.0        12.0    22.0                                         C45AS        8.0         7.0     7.0                                          Silicate     --           1.0    5.0                                          Soap         --          --      2.0                                          Brightener 1 0.2         0.2     0.2                                          Carbonate    8.0         16.0    20.0                                         DTPMP        --          0.4     0.4                                          Spray On                                                                      C45E7        1.0         1.0     1.0                                          Dry additives                                                                 PVPVI/PVNO   0.5         0.5     0.5                                          Protease     1.0         1.0     1.0                                          Lipase       0.4         0.4     0.4                                          Amylase      0.1         0.1     0.1                                          Cellulase    0.1         0.1     0.1                                          NOBS         --          6.1     4.5                                          Percarbonate 3.0         7.0     8.0                                          Sodium sulfate                                                                             --          6.0     --                                           Balance (Moisture                                                                          100         100     100                                          and Miscellaneous)                                                            ______________________________________                                    

Example 10

The following high density and bleach-containing detergent formulations,according to the present invention were prepared:

    ______________________________________                                                   P'        Q'      R'                                               ______________________________________                                        Blown Powder                                                                  STPP         15.0        15.0    15.0                                         MGDA         2.0         2.0     2.0                                          Sodium sulfate                                                                             0.0         5.0     0.0                                          LAS          3.0         3.0     3.0                                          QAS          --           1.5    1.5                                          DTPMP        0.4         0.4     0.4                                          CMC          0.4         0.4     0.4                                          MA/AA        4.0         2.0     2.0                                          Agglomerates                                                                  LAS          5.0         5.0     5.0                                          TAS          2.0         2.0     1.0                                          Silicate     3.0         3.0     4.0                                          Zeolite A    8.0         8.0     8.0                                          Carbonate    8.0         8.0     4.0                                          Spray On                                                                      Perfume      0.3         0.3     0.3                                          C45E7        2.0         2.0     2.0                                          C25E3        2.0         --      --                                           Dry additives                                                                 Citrate      5.0         --      2.0                                          Bicarbonate  --          3.0     --                                           Carbonate    8.0         15.0    10.0                                         TAED         6.0         2.0     5.0                                          Percarbonate 16.0        9.0     12.0                                         Mn Catalyst  0.1         --      --                                           Polyethylene oxide                                                                         --          --      0.2                                          of MW 5,000,000                                                               Bentonite clay                                                                             --          --      10.0                                         Protease     1.0         1.0     1.0                                          Lipase       0.4         0.4     0.4                                          Amylase      0.6         0.6     0.6                                          Cellulase    0.6         0.6     0.6                                          Silicone antifoam                                                                          5.0         5.0     5.0                                          Dry additives                                                                 Sodium sulfate                                                                             0.0         3.0     0.0                                          Balance (Moisture                                                                          100.0       100.0   100.0                                        and Miscellaneous)                                                            Density (g/liter)                                                                          850         850     850                                          ______________________________________                                    

What is claimed is:
 1. A bleaching composition consisting of:(a) apercarbonate bleach compound which is stabilized with a coating materialwhich is a mixed salt of sodium sulphate and sodium carbonate; and (b)an amino tricarboxylic acid or salt thereof wherein said aminotricarboxylic acid has the general formula: ##STR23## where R₁, R₂ andR₃ are alkyl groups or substituted alkyl groups of chain length C1 toC4; n is 0 or 1; and X is an organic substituent group.
 2. A bleachingcomposition according to claim 1 wherein said percarbonate bleach issodium percarbonate of formula 2Na₂ CO₃.H₂ O₂.
 3. A detergentcomposition according to claim 1 wherein said amino tricarboxylic acidis methyl glycine diacetic acid.
 4. A method for cleaning soiledtableware comprising treating said tableware with an aqueous liquidhaving dissolved or dispensed therein a composition according to claim 1in a machine dishwasher.
 5. A method for cleaning soiled laundrycomprising treating said laundry with an aqueous liquid having dissolvedor dispensed therein a composition according to claim 1 in a washingmachine.
 6. The bleaching composition of claim 1, wherein thepercarbonate bleach compound comprises from 2 percent to 30 percent byweight of the composition.
 7. The bleaching composition of claim 1,wherein the percarbonate bleach compound comprises from 3 percent to 20percent by weight of the composition.
 8. The bleaching composition ofclaim 1, wherein the amino tricarboxylic acid comprises from 0.01percent to 40 percent by weight of the composition.
 9. The bleachingcomposition of claim 1, wherein the amino tricarboxylic acid comprisesfrom 0.1 percent to 15 percent by weight of the composition.